Quaternary ammonium compound and method of making same



Patented May 9, 1944 QUATERNABY AlllMIONIUM COLIPOUND AND METHOD OF MAKING SAIHE Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assiznors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Original application October 20,

1941, Serial No. 415,766.

Divided and this application June 3, 19 3, Serial No. 489,573

6 Claims. (01. 260287) This invention relates to a new chemical compound.

One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, and also capable of use for various other purposes. For instance, the material may be used as a break inducer in doctor treatment of the kind intended to sweeten gasoline. Certain of the compositions of matter herein described are of value as surface tension depressants in the acidification of calcareous oil-bearing strata by means of strong mineral acid, such as hydrochloric acid. Simi: larly, some members are effective as surface tension depressants, or wetting agents in the flooding of exhausted oil-bearing strata.

Another object of our invention is to provide a novel method for producing said new material or composition of matter.

The new composition of matter herein described consists of aquaternary compound of the Pyridine series of the kind hereinafter describedv in detail. Members of the pyridine series suit-' able as reactants include pyridine,- alkylated derivatlves of pyridine, particularly alkylated derivatives, in which the alkyl radical contains three carbon atoms or less, and especially methylated pyridines, i. e., pyridines, in which one, two, or three methyl "groups have been substituted in the nucleus, such-as picolines, luti-' V into the individual components.

Specifically, then, the compounds herein contemplated as demulsifiers consist of the quaternary nitrogen products obtained by reacting one mole of hydroxy compounds (substituted lactwherein T is a hydrocarbon radical having at least 8 and not more than 32 carbon atoms, and T' is a hydrogen atom, a hydrocarbon radical ,having less than 8 carbon atoms, or the same as T, with a heterocyclic compound of the pyridine series selected from the group consisting of pyridine, quinoline, isoquinoline', and C-methyl homologues thereof, in the presence of substantially one mole of halogen hydride at an elevated temperature, the heterocyclic compound being applied in an amount substantially equivalent to the halogen hydride, and usually in excess thereof, i. e., thereaction being conducted in the presence of the free base.

As to primary or secondary amines having at least 8 and not more than 32 carbon atoms, and which are suitable for reaction with lactic acid or its functional equivalent, for instance, ethyl lactate, reference is made to U. S. Patent No. 2,246,842, dated June 24, 1941, to De Groote. It is to be noted that that particular patent excludes arylamines; but, it is understood that such compounds are not excluded in the present instance. For instance, naphthylamine, methyl naphthylamine, ethyl naphthylamine, and the like, may be employed.

Furthermore, attention is directed to the fact that said aforementioned De Groote patent contemplates, inter alia, certain tertiary amines. Such amines, of course, are not herein contemplated as reactants, insofar that there is no reactive hydrogen( atom available.

The primary amines which may be used as such or converted into secondary amines by conventional processes, such as treatment with methyl iodide, benzyl chloride, alkyl sulphates, or the like, include the following: octadecenylamine; cetylamine; stearylamine; oleoamine; ricinoleoamine; amines derived from naphthenic acids; amines derived from octadecadiene 9,11- acid-l; octadecylamine; amines derived from mixed unsaturated fatty acids, such as soyabean fatty acids; cottonseed oil fatty acids; linseed oil fatty acids; heptadecylamine, hexadecylamine; dodecylamine; decylamine, etc. The amines may be aliphatic, aralkyl, alicyclic, aryl, alkyl, etc.

One mayalso employamines derived from acids obtained by oxidation of wax, parafiin, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No.

fligififi'lz idat u May 20, 1941, to Shields. The following patents listed in the aforementioned De Groote Patent No. 2,246,842, are hereinincluded as a matter of convenience indicating means of obtaining such high molal primary or secondary amines or methods which can be obviously modified to produce the same:

Dated Patentee U. 8. Patent No 1,951,469.... Mar. 20,1934 Bertsch 2,006,0 June 25,1935 Olin 2,033,866...- Mar. 10,1936 Schrauth 2,074.3 Mar. 23,1937 Flatt .078, May 4,1937 Arnold 2,091,105- Aug. 24,1937 Pigott 2,108. 7. Feb. 15,1918 Spear 2,110.1 Mar. 8,1938 Carothars 2,132,902--- Oct. 11,1938 nher 178.5 Oct. 31,1938 Ralston British Patent No .001 1932 Johnson 358,114 1932 Carpmael Having obtained a high molal amine of the kind described, it is reacted with lactic acid, or its functional equivalent, and most preferably, with a lactic acid ester, for instance, methyl lactate, ethyl lactate, propyl lactate, etc. Such reaction ,results in'the formation of a substituted lactamide, as indicated by the following:

HC-C .IO 6 H; HiNT H 7 n: een He -sworn HiNT H The substituted'lactamides thus obtained are reacted with' pyridinefl hydrochloride or a halide of any of the heterocyclic bases previously de-. scribed, or'mixtures thereof. Such reactions may be indicated in the following manner:

c 'r Na"'r6s-. t1v

Our preferred reactants are: octadecyllactamide;

cetyllactamide:' stearyllactamide; hydroxydecyl The" mechanical procedure employed is substantially the" same ,asusedfin connection with another typejjof, reactioninvolving the formation of quaternaryfcompounds by th elimination of water. 'See U. S. Patent No. 2,242,211, dated May 19 1...to 'Haacl. See' also U. s. Patent No. 2,27,3,18lj, 'dated ebruar 17, 1942, to De. Groote and Kaiser. The compounds or compositions of atter intended tobeus'ed asfthe demulsifler of our process maybeexemplified by the following examples retailer reaction between octylamine and ethyl lactate) is reacted with 1.1 pound moles of pyridine hydrochloride in the presence of /20 of a mole of free pyridine. The reaction is conducted at approximately ISO-160 C., until the substituted lactamide has been converted into the quaternary compound. This reaction is complete in a comparatively short time, in some instances, less than one hour, although in other instances three or four hours may be required. If desired the reaction may be conducted at a slightly higher temperature, for instance, as high as 180 C. Instead of using pyridine hydrochloride, one may employ the hydrochloride of a fraction of pyridine-bases of the kind that 50% will distil over at" 0., or below, and 90%, at C. or below. Such selected pyridine bases are of the. kind which are entirely water-soluble.

Example 2 Octadecenyllactamide is substituted for octyllactamide in Example 1, preceding.

Example 3 Octadecyllactamide is substituted for octyllactamide in Example 1, preceding.

Example 4 Dodecyllactamide is substituted for octyllactamide in Example 1, preceding.

Example 5 Decyllactamide is substituted for octyllactamide in Example 1, preceding.

Example 6 The substituted lactamide derived by reaction Unsaponifiable matter per cent.--

Water by distillation do 1.0 Saponification number 229.0 Neutralization number 223.0 to 228.0 Ash per cent 0.76

are converted into amines in the conventional manner, and such naphthenylamine is reacted with ethyl lactate to obtain the corresponding substituted lactamide, instead of octyllactdmide,

in Example 1, preceding.

The manufacture of the above compounds is usually conducted with an excess of the pyridinium halide, such as the hydrochloride, or hydrobromide, and usually, in the presence of a significant amount of the free pyridinium basalt self. In many instances, however, there is no need to use an excess of the pyridinium base halide, and, in fact, no need to have present any of the free pyridi'nium base itself, or, at the most, onlya trace of the free base.

Sometimes thereaction with the pyridinium compound can be catalyzed by the presence of small amounts of soaps or alkalies. As is obvious, other monovalent anions may replace the halogen and serve as a functional equivalent.

A somewhat analogous use of our demulsifying agent is the removal of a residual mud sheath which remains after drilling a, well by the rotary method. Sometimes the drilling mud contains added calcium carbonate or the'like to render aerpqu damole f-octyllactamid de ed by n the mud susceptible'to reaction with hydrochloric acid or the like, and thus expedite its removal.

formula:

aseaeie It has been pointed out that the present in-- vention is concerned not only with chemical compounds for breaking petroleum emulsions of the water-in-oil type in various forms, as already 2,273,181, dated February 17, 1942, to De Groote and Keiser. Said patent contemplates resolution of petroleum emulsions of the water-in-oil type by means of demulsifiers Of the following formula type:

Halogen in which the acyl radical RC is derived from a monocarboxy detergent-forming acid having at least 8 carbon atoms and not more than 32 carbon atoms; and DEN represents a heterocyclic compound of the pyridine,series consisting of pyridine, quinoline, isoquinoline, and C-methyl homologues thereof. The halogen, of course, is most suitably chloride or bromine; but iodine may be employed except for its excessive cost. More correctly, DEN is contemplated as a radical, rather than a compound.

Attention is also directed to our copending applications, filed the same date as the instant application, and bearing the following serial numbers: 415,763, 415,764 and 415,765.

The present application is a division of our pending application Serial No, 415,766, filed Oct. 20, 1941.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A new chemical compound of the following Halogen n i 0 'r -lin/ non 'r' DEN isoquinoline, and C-linked methyl homologues thereof.

3. A new chemical compound of the following formula:

Halogen DEN O 'l non n wherein Tis an alkyl radical having at least 8 and not more than 32 carbon atoms: and DEN represents a heterocyclic compound of the pyridin eries consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

4. A new chemical compound of the following formula:

' Halogen wherein T is an alicyclic radical having at least 8 andnot more than 32 carbon atoms; and DEN gen atoms and hydrocarbon radicals having not more than 32 carbon atoms; and DEN represents a heterocyclic compound of the pyridine series wherein T is a hydrocarbon radical having at least 8 andnot more than 32 carbon atoms: and

DEN representsa heterocyclic compound of the pyridine series consisting of pyridine, quinoline,

represents a heterocyclic compound of the pyridine series consisting of pyridine, qliinoline, isoquinoline, and C-linked methyl homologue; thereof.

5. A new chemical compound of the following,

- formula:

Halogen DEN\H I C-(QN BAH H wherein T is an aryl radical having at least 8 and not more than 32 carbon atoms; and DEN represents a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof. V

6. A method for manufacturing chemical compounds of the following formula ty'pe:

Halogen wherein T is a hydrocarbon radical having at least 8 and notmore than 32 carbon atoms, and T is a member of the class consisting of hydrogen atoms and hydrocarbon radicals having not more than 32 carbon atoms: and DEN represents a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and .C-linked methyl homologues thereof; said method involving the step of reacting a substituted lactamide of the following type:

. in which '1 and'i." have their prior significance. 

